Souhir Abid

Novel Synthesis of 2‐Oxo‐2H‐Benzopyrano[2,3‐d]Pyrimidines

Abstract The synthesis of novel substituted 3‐cyanoiminocoumarins and corresponding N‐ethoxycarbonyl iminocoumarins is described. The condensation of N‐ethoxycarbonyl‐3‐cyano‐7‐diethylamino iminocoumarin with amines as N‐nucleophiles yields substituted 2‐oxo‐2H‐benzopyrano‐[2,3‐d]pyrimidines having promising optical properties.

Polyterephthalates Bearing Bio-based Moieties

Dimethyl terephthalate was reacted with 5,5′-Isopropylidene-bis(ethyl 2-furoate), 1,4:3,6-dianhydrohexitols and ethan-1,2-diol in order to obtain PET incorporating bio-based moieties. Polycondensation was achieved in two steps: (i) the formation of a hydroxyethyl-terminated oligomer by reaction of starting diester mixture with excess ED and, (ii) a polycondensation step with elimination of ED was used to obtain high molar mass copolyesters. Copolymers of various compositions were synthesized and characterized by 1H-NMR, SEC, DSC and TGA. The resulting materials are amorphous polymers (T g = 104–127 °C) with good thermal stability.

New Copolyesters Containing Aliphatic and Bio-Based Furanic Units by Bulk Copolycondensation

A straightforward substitution of non-renewable aromatic aliphatic copolyesters by renewable homologous furanic aliphatic copolyesters was successfully realized by copolymerization of furanic unit, aliphatic and 1,3-propanediol. Different copolyesters were synthesized and characterized by 1H-NMR, 13C-NMR, FTIR, DSC and TGA. For all copolyesters, the degree of randomness, determined by 1H-NMR, was close to 1, reflecting a random distribution of furanic and aliphatic ester units in polymer chains. The hydrolytic degradation of polymers was performed at pH 4.35 at 37°C over a period of four weeks. The hydrolytic degradation proved a mass loss of about 10%.

One-step Synthesis of PCL-Urethane Networks using a Crosslinking/de-crosslinking Agent

Thermally reversible cross-linked polycaprolactone-urethane (PCL-U) was prepared in one-step procedure. The PCL-U networks were synthesized from a di-isocyanate (4,4′-methylene bis(cyclohexylisocyanate) (HMDI) and hydroxyl bearing macromers and monomers: hydroxy-terminated PCL, glycerol and a di-alcohol Diels-Alder (DA) adduct. This adduct was used to introduce both diene and dienophile functions in the structure and also to protect the maleimide functions from polymerization. The thermoresponsive behavior of the material was characterized by commonly used methods such as solubility tests at different temperatures and differential scanning calorimetry analyses to highlight rDA reactions and also by rheological analysis. The effects of the cooling rate, the molar mass of polycaprolactone as well as the molar ratio [di-Isocyanate]/[PCL-diol] on the cross-linking/de-cross-linking temperatures were also analyzed. The reversible networks obtained have a self-healing behavior.

Small Iminocoumarin Derivatives as Red Emitters: From Biological Imaging to Highly Photoluminescent Non‐doped Micro‐ and Nanofibres

The fluorescence properties of four derivatives of 3-thienyl-2-(N-dicyanovinyl)iminocoumarin, bearing a diethylamino group in the 7-position or a methoxy group in the 6, 7 and 8 positions, were compared in solution and in the solid state. The 7-diethylamino derivative was strongly fluorescent in various solvents, with marked solvatochromism. Its fluorescence was quenched by aggregation. In contrast, the methoxy derivatives were only moderately or weakly fluorescent in solution, but two of them were strongly photoluminescent in the crystalline state, owing to favourable molecular packing. The 6-methoxy derivative even exhibited spectacular crystallization-enhanced emission, examples of which are particularly rare for this type of dyes. Dyes were tested for biological use. The 7-diethylamino derivative led to particularly strong fluorescence staining of the cytoplasm of HCT-116 colon cancer cells. No fading was observed over prolonged illumination by the microscope light beam, but a phototoxic effect was detected. The use of the dyes as red-emitting materials was also investigated. Using easy-to-implement preparation methods, the compounds self- assembled to give one-dimensional nano- and microsized particles, including millimeter-long microfibres that exhibited clear wave-guiding properties. This study shows the value of these low molecular-weight molecules for the preparation of new orange and red-emitting fluorescent materials based on totally pure dye.

Synthesis of Primary Amines by One-Pot Reductive Amination of Aldehydes

Abstract We report here a novel, one-pot, two-step reductive amination of aldehydes for the atom-economical synthesis of primary amines. The amination step has been carried out with hydroxylammonium chloride and does not require the use of a base. In the subsequent reduction step, a metal zinc/hydrochloride acid system has been used. This method is applicable to both aliphatic and aromatic aldehydes. The operational simplicity, the short reaction times, and the mild reaction conditions add to the value of this method as a practical alternative to the reductive amination of aldehydes. Supplemental materials are available for this article. Go to the publishers online edition of Synthetic Communications® to view the free supplemental file. GRAPHICAL ABSTRACT

Polyazomethines Bearing Furan Moieties. Solution Polycondensation of Bis(furanic diamine)s and Aromatic Dialdehydes

A series of new polyazomethines containing furan moieties was synthesized by polycondensation of bifuranic diamine monomers with commercially available aromatic dialdehydes viz., terephthaldehyde (TPA), isophthaldehyde (IPA). Inherent viscosities and number average molecular weights of polyazomethines were in the range 0.90–1.56 dL/g and 10460–17850 (SEC, polystyrene standard), respectively indicating formation of medium to reasonably high molecular weight polymers. The resulting polyazomethines were characterized by solubility tests, viscosity measurements, FTIR, NMR, UV spectroscopy, differential scanning calorimetric (DSC), and thermogravimetric analysis (TGA). These furan-based polyazomethines were essentially amorphous and exhibited glass transition temperatures (Tg) in the 150–190°C range. The temperature at 10% wt loss (T10), determined from TGA of polyazomethines were in the range 300–380°C, indicating their good thermal stability.

Synthesis of 2-Amino-4-(2-hydroxynaphthyl)-4H-chromene-3-carbonitriles by Michael Addition and Their Transformation into New Pentacyclic Compounds

Abstract 2-Amino-4-(2-hydroxynaphthyl)-4H-chromene-3-carbonitriles were synthesized by Michael addition of various 3-cyanoiminocoumarins and β-naphthol in good yield. The heterocyclization of these materials in an acidic medium leads new heterocyclic compounds, which have not previously been described, in moderate to good yields and good selectivity. The synthesized compounds were characterized by infrared, 1H NMR, 13C NMR, two-dimensional NMR, and elemental analysis. GRAPHICAL ABSTRACT

Simple and convenient access to α,α,α-trisubstituted amides by double addition of Grignard reagents to acyl cyanohydrins

The double addition of Grignard (alkyl, aryl, alkenyl, alkynyl) reagents to acyl cyanohydrins was performed under unusually smooth conditions with a concomitant O-N acyl transfer, providing a very simple and general access to α,α,α-trisubstituted amides.

Synthesis of New Iminocoumarins Bearing Parabanic Moieties

Abstract The synthesis of novel substituted 3-p-nitro-phenyliminocoumarins and corresponding N-ureaiminocoumarins is described. The condensation of these materials with oxalyl chloride leads to the corresponding N-parabanic iminocoumarins, which have not previously been described, in moderate or good yields and high selectivity. The structures were characterized by Fourier transform infrared, 1H and 13C NMR, and elemental analysis.